Syntheses of host molecules and evaluation for lithium ion recognition

主体分子的合成及锂离子识别评价

• 批准号: 09640697
• 负责人: AKABORI Sadatoshi
• 金额: $ 0.64万
• 依托单位: Toho University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640697/
• 关键词: Hosut-Gest; Calixarene; homooxisacalixarene; Selecticity of Lithium; Alkali metal ion; alkali earth metal ion; phosphoric acid functional group; ホスト-ゲスト; ホスト-ゲスト化学; リチウムイオン選択性; ホモオキサカリックス[3]アレーン; 挿入反応; リン酸基修飾カリツクスアレーン; ホストーゲスト化学

Phosphate diesters, 1a, 1b, and 1c, having p-tert-butylcalic[4]arenes and alkyl groups (methyl, ethyl and propyl groups) as ester moieties were prepared. These compounds exist as an equilibrium of cone and partial-cone conformations in solution. However, the conformations of the calix[4]arene moieties in the Li and Na complexes of 1a as the methyl ester and/or 1b as the ethyl ester in solution are cone only, although that of the K complexes exist as a mixture of cone and partial-cone conformers. The compounds 1a, 1b, and 1c showed selective complexation abilities toward the Li cation based on liquid membrane transport experiments. Liquid membrane transport abilities of alkali metal cations using 1a depend upon the pH in the source phase. By increasing the pH, higher transport abilities for alkali metal cations and higher selectivity for LiィイD1+ィエD1 were observed. Furthermore, in order to obtain the phosphate ester having hexahomooxacalix[4]arene the reaction of hexahomooxacalix[4]arene with phosphorous tichloride was carried out. However the unexpected product was obtained. Therefore, the structure and formation mechanism of the unusual product were investigated in details.

制备具有对叔丁基杯[4]芳烃和烷基（甲基、乙基和丙基）作为酯部分的磷酸二酯1a、1b和1c。这些化合物在溶液中以锥形和部分锥形构象的平衡形式存在。然而，在溶液中的锂和钠络合物1a作为甲酯和/或1b作为乙酯的杯[4]芳烃部分的构象是仅锥形的，尽管K络合物的构象以锥形和部分锥形构象的混合物存在。基于液膜传输实验，化合物1a、1b和1c显示出对Li阳离子的选择性络合能力。使用1a的碱金属阳离子的液膜传输能力取决于源相中的pH。通过增加pH值，观察到对碱金属阳离子的更高的传输能力和对Li_xD_1 + Li_xD_1的更高的选择性。此外，为了获得具有六高氧杂杯[4]芳烃的磷酸酯，进行了六高氧杂杯[4]芳烃与三氯化磷的反应。然而，获得了意想不到的产物。因此，对该异常产物的结构和形成机理进行了详细的研究。

项目成果

S.Akabori et al.: "Syntheses of phosphate diesters having p-tert-butylcalix[4]arene and alkyl group as ester moieties, and their selective lithium cation transport abilities througy liquid membranes"Chemical Communications. No22. 2137-2138 (1999)

S.Akabori 等人：“具有对叔丁基杯[4]芳烃和烷基作为酯部分的磷酸二酯的合成，及其通过液膜的选择性锂阳离子传输能力”《化学通讯》。

S. Akabori: "Syntheses of phosphate diesters having p-tert-butylcalix[4]arene and alkyl group as ester moieties, and their selective lithium cation transport abilities through liquid membranes"Chemical Communications. NO.22. 2137-2138 (1999)

S. Akabori：“具有对叔丁基杯[4]芳烃和烷基作为酯部分的磷酸二酯的合成，及其通过液膜的选择性锂阳离子传输能力”《化学通讯》。

S.Akabori: "Syntheses of phosphate diesters having p-tert-butylcalix[4]areneand alkyl group as ester moieties,and their selective lithium cation transport abilities through liquid membranes" Chemical Communications. No.22. 2137-2138 (1997)

S.Akabori：“具有对叔丁基杯[4]芳烃和烷基作为酯部分的磷酸二酯的合成及其通过液膜的选择性锂阳离子传输能力”化学通讯。

S.Akabori: "Syntheses of phosphate diesters having p-tert-butylcalix[4]arene and alkyl group as ester moieties,and their selective lithium cation transport abilities through liquid membranes"Chemical Comunications. No.22. 2137-2138 (1999)

S.Akabori：“具有对叔丁基杯[4]芳烃和烷基作为酯部分的磷酸二酯的合成及其通过液膜的选择性锂阳离子传输能力”《化学通讯》。

S.Akabori: "Syntheses of phosphate diesters having p-tert-butylcalix[4]areneand alkyl group os oster moictics,and their selective lithium cation transport abilities through liquid membranes" Chemical Communications. No.22. 2137-2138 (1997)

S.Akabori：“具有对叔丁基杯[4]芳烃和烷基基团的磷酸二酯的合成，及其通过液膜的选择性锂阳离子传输能力”化学通讯。